Promoting stability of sub-3 nm In2S3 nanoparticles via sulfur anchoring for CO2 electroreduction to formate

doi:10.1016/S1872-2067(24)60233-0

Abstract

Abstract:

The p-block metal (In, Sn, Bi, etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO₂ reduction (ECR) to formate. However, the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications. Herein, we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In₂S₃ nanoparticles on sulfur-doped porous carbon substrates (i-In₂S₃/S-C) for formate production. Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction (MSSI), which effectively regulated the electronic states of In₂S₃, achieving a high formate Faradaic efficiency of 91% at −0.95 V vs. RHE. More importantly, the sulfur anchoring effectively immobilized the sub-3 nm In₂S₃ nanoparticles to prevent them from agglomeration. It enabled the catalysts to exhibit much higher durability than the In₂S₃ samples without sulfur anchoring, demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In₂S₃ catalysts. These results provide a viable approach for developing efficient and stable electrocatalysts for CO₂ reduction.

Key words: Electrochemical CO₂ reduction, Strong metal sulfide-support, interaction, In₂S₃ nanoparticles, Stability, Formate

Fanrong Chen, Jiaju Fu, Liang Ding, Xiaoying Lu, Zhe Jiang, Xiaoling Zhang, Jin-Song Hu. Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate[J]. Chinese Journal of Catalysis, 2025, 71: 138-145.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60233-0

https://www.cjcatal.com/EN/Y2025/V71/I4/138

Figures/Tables 5

Fig. 1. (a) Schematic synthesis process of the i-In2S3/S-C catalyst. (b) TEM image of S-C support. TEM image (c), corresponding size distribution (d), and the HRTEM image (e) of the i-In2S3/S-C catalyst. (f) XRD patterns of i-In2S3/S-C, l-In2S3/S-C, and i-In2S3/C catalysts. (g) EDS elemental mapping of i-In2S3/S-C.

Fig. 2. The In and S atomic contents (a) and high-resolution XPS spectra of In 3d (b) and S 2p (c) in i-In2S3/S-C, l-In2S3/S-C, and i-In2S3/C catalysts. The in-situ temperature-programmed XRD patterns of i-In2S3/S-C (d) and the corresponding temperature-dependent Normalized FWHM with derivatives for In2S3 (311) diffraction peak (e) and the UPS spectra (f) of i-In2S3/S-C, l-In2S3/S-C, i-In2S3/C.

Fig. 3. (a) LSV curves of i-In2S3/S-C, l-In2S3/S-C, i-In2S3/C, and S-C at a scan rate of 10 mV s?1. (b) The potential-dependent product distributions of i-In2S3/S-C catalyst. The potential-dependent FEformate (c), jformate (d), formate formation rates (e), and the Tafel plots (f) of the i-In2S3/S-C l-In2S3/S-C and i-In2S3/C.

Fig. 4. Stability test at ? 0.95 V vs. RHE of i-In2S3/S-C, l-In2S3/S-C and i-In2S3/C.

Fig. 5. (a) XRD patterns of i-In2S3/S-C, l-In2S3/S-C and i-In2S3/C after long time ECR test at ? 0.95 V vs. RHE. (b) EDS mapping image of i- In2S3/S-C after 75 h ECR test at ? 0.95 V vs. RHE. S 2p (c) and In 3d (d) XPS spectra of i-In2S3/S-C before and after long time ECR test at ?0.95 V vs. RHE.

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Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate

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